Means for making textiles water resistant



United States Patent cc 3,148,164 MEANS FOR MAKING TEXTILES WATER RESISTANT Heinz Werner Enders, Stadtbergen, near Augsburg, and

Hans Deiner and Eugen Walter Kurz, Augsburg, Germany, assignors to Chemische Fabrlk Pfersee G.m.h-H., Augsburg, Germany, a firm of Germany No Drawing. Filed July 31, 1961, Ser. No. 127,906 Claims priority, application Germany Apr. 21, 1961 7 Claims. (Cl. 260-214) This invention relates to textile finishing, and is more particularly concerned with the treatment of textile materials to improve their water resistance.

The latter term is being employed to include the reduced water absorption of cellulosic fibers such as rayon obtained by means of textile treating compositions of this invention which causes treated rayon to shrink less than rayon not treated by such compositions. The term water resistance as used hereinafter will also be understood to include water repellancy, the hydrophobic properties of the fibers of a fabric which retard or prevent passage of water through the fabric.

More specifically, this invention is concerned with an improvement in known textile treating compositions based on N-alkyl-N,N-alkylene derivatives of urea, wherein the alkyl radical of the urea derivative has at least ten, and usually twelve or more carbon atoms, and the alkylene radical has two or three carbon atoms. Such urea derivatives are known to impart to fabrics not only'improved water resistance, but also a very desirable soft hand.

The afore-mentioned urea derivatives are insoluble in water, and they are applied to fabric in the form of aqueous dispersions which are stabilized by the addition of alkaline compounds intended to prevent precipitation of the dispersed phase under the acidifying influence of atmospheric carbon dioxide.

The alkaline compounds employed as stabilizers for the urea derivative dispersions may be non-volatile or more or less volatile. If volatile alkaline stabilizers are used, compounds having the formula X-O-CH -YZ, wherein X is an alkyl radical having more than ten, and preferably 11 to 22 carbon atoms, Y is a pyridine or oxyethylmorpholine and Z is the'monovalent radical of an acid is simultaneously used. 15 to 40 percent, and preferably 20 to 30 percent of this compound, calculated on the urea derivative, are employed.

We now have found that the stability of such emulsions may be furtherimproved very substantially by the addition of certain aminotriazine pre-condensates. The aminotriazine pre-condensates of the invention are insoluble in water, but soluble in dilute aqueous solutions of lower monocarboxylic alkanoic acids. They contain at least two amino radicals attached to the triazine ring which is free of directly attached hydroxyl groups. They are obtained by condensing an aminotriazine with formaldehyde and a lower monohydric alkanol having one to five carbon atoms, and the condensation product contains per triazinyl radical at least one aliphatic radical containing more than ten carbon atoms, and preferably eleven to twenty-two carbon atoms, and at least 0.2 equivalent of a basic amino radical of an alkanolamine of the formula R1TIR1 R2 wherein R is hydrogen, a lower alkyl radical having between one and four carbon atoms, a hydroxyalkyl radical having two to four carbon atoms, or a radical of the formulas CH CH -NR R 3,148,164 Patented Sept. 8, 1964 R is a hydroxyalkyl radical having two to four carbon atoms; and R is hydrogen or a hydroxyalkyl radical of two to four carbon atoms.

The aminotriazine pre-condensates of our invention are added to the afore-mentioned emulsions in the form of solutions of the aminotriazine tire-condensates in liquid organic solvents which are substantially insoluble in water and do not contain free hydroxyl radicals. The concentration of the organic solutions is preferably between 25 carbon atoms, six to eighteen mols, and preferably nine to fifteen mols of paraformaldehyde, 0.2 to 1.2 mols, and preferably 0.5 to 1.0 mol of an aminoalkanol, preferably of the formula Ra III-Rb wherein R, is hydrogen or a hydroxyalkyl radical having two to three carbon atoms, and R and R are hydroxyalkyl radicals having two to three carbon atoms, and with a lower monohydric alkanol having one toflve carbon atoms to a temperature of to 140 C. while volatile constituents of the reaction mixture are permitted to distill olf. Heating is continued until the precondensate formed is soluble in dilute monocarboxylic acids, and preferably in hot aqueous 5 to 10 percent acetic acid.

The monocarboxylic acid having more than ten carbon atoms may be replaced in the above reaction by an equivalent amount of the corresponding anhydride, that is, by one half to one mol of the anhydride.

Pre-condensates of the same type are arrived at when the aminotriazine and the aliphatic monocarboxylic acid having more than ten carbon atoms or its anhydride are replaced in the above reaction by one mol of a melamin derivative wherein one to three hydrogen atoms of the amino radicals are replaced by aliphatic acyl radicals having more than ten carbon atoms, and preferably fifteen to nineteen carbon atoms.

According to another method, methylol aminotriazines and particularly methylol melamines the alkylol groups of which are etherified with lower monohydric alkanols having one to four carbon atoms are used as starting materials. One mol of an etherified methylol melamine or its equivalent is reacted with one to two mols of an aliphatic monocarboxylic acid having more than ten, and preferably fifteen to nineteen carbon atoms at a temperature between and 200 C. Heating is preferably continued until substantially all the fatty acid is combined. The reaction may be performed at ambient pressure or in a vacuum. The intermediate product obtained is further reacted with 0.2 to 1.2 mols, and preferably 0.5 to 1.0 mol of an aminoalkanol, preferably of the formula a vacuum. Heating is continued until the pre-condensate formed is soluble in dilute aqueous formic or acetic acid.

In yet another method of preparing the precondensates of the invention, one mol of a 2,4-diarnino-6-alkyl-1,3,5- triazine is heated jointly with paraformaldehyde, and preferably with five to eight mols of paraformaldehyde, with 0.2 to 1.2 mol, and preferably with 0.4 to 1.0 mol of an aminoalkanol which preferably conforms to the above formula, and with a lower, monohydric alkanol having one to five carbon atoms, to a temperature between 130 and 160 C. while volatile constituents of the reaction mixture are permitted to distill oi'f. Heating to such a temperature is continued until the pre-condensate formed is soluble in dilute aqueous lower alkanoic acids, and particularly in hot, 5 to percent acetic acid.

A further method of synthesizing the pre-condensates of the invention starts with an aminotriazine derivate obtained by heating a compound of the formula wherein Z is hydrogen, amino radical, alkyl radical with 1 to 22 carbon atoms; with at least 1 mol of an alkyl isocyanate per mol of said aminotriazine derivate and at most 1 mol of said alkyl isocyanate per equivalent amino radicals, to a temperature of 200 to 260 alkylisocyanate has more than ten, and preferably to 19 carbon atoms. Especially used are derivatives obtained by heating one mol of melamine with 1.2 to 2 mols of said alkyl isocyanate. One mol of said aminotriazine derivative is reacted with 6 to 18, and preferably 9 to 15 mols paraformaldehyde, 0.2 to 2 mols, and preferably 0.7 to 1.5 mols of an aminoalkanol which preferably has the above-indicated formula, and with a lower monohydric alkanol having at most five carbon atoms, at temperatures between 130 and 160 C. while permitting volatile constituents to distill from the reaction mixture. Heating is continued until the precondensate is soluble in dilute monocarboxylic alkanoic acids, and particularly in hot five to ten percent aqueous acetic acid.

The test for completion of the precondensation reaction may be performed most conveniently with 5 to 30 percent aqueous solutions of formic or acetic acid, by adding the pre-condensation product to the hot solution of the carboxylic acid, or by adding the pro-condensate to the acid solution in the cold, and by heating the mixture.

The substantially water insoluble liquid organic solvents which do not contain free hydroxyl radicals and are employed as diluents for the pre-condensates of the invention may be chlorinated hydrocarbons, such as carbon tetrachloride or trichloroethylene, or non-chlorinated hydrocarbon such as gasoline, benzene, toluene, or tetrahydronaphthalene. These solvents may also be employed in mixtures having preferably a specific gravity of approximately one for better stability of the emulsions formed. The solvents are preferably employed in amounts equal to the weight of the acid soluble basic precondensates dissolved therein.

Dispersions of the known N-alkyl-N',N-alkylene ureas become highly viscous in storage. It is difilcult, if at all possible, to dilute the very viscous dispersions with water to the concentration required for the treatment of textile materials. It is characteristic of the usual dispersions of alkyl-alkylene ureas that the dispersed material is precipitated when the dispersion is diluted. When such diluted dispersions are applied to fabric on a padding machine, the precipitate coats the rolls and interferes with continuous operation of the machine. It may also be transferred to the fabric and result in stains.

When mixtures of the acid soluble pre-condensates of 3T1: allzyl radical has more than 10, particularly 11-22 carbon atoms.

C. The

the invention with solvents are added to dispersions of N-alkyl-N',N'-alkylene ureas, the dispersions may be readily diluted even after prolonged storage. Dispersions may be made capable of ready dilution by the addition of a mixture of a basic pro-condensate of the invention with a suitable solvent when the dispersions already have become very viscous by aging and cannot readily be diluted without such an addition.

The addition of the pre-condensate solution does not prevent the increase in viscosity during storage, nor does the addition of the pre-conclensate solution reduce the viscosity of an aged alkyl-alkylene urea dispersion. Yet, these viscous dispersions are readily diluted with water in the presence of the precondensates of the invention, and harmful precipitation of N-alkyl-N',N-alkylene urea is prevented.

The treating baths prepared from mixtures of alkylalkylene ureas with the pre-condensates of the invention are compatible with optical bleaches or brighteners to an astonishing extent whereas the dilute dispersions of N- alkyl N,N'-alkylene ureas are well known not to be compatible with such brighteners.

The treating baths containing the pre-c'ondensates of the invention are less sensitive than usual alkyl-alkylene urea baths to electrolytes such as salts of polyvalent metals in the presence of conventional finishing agents employed for improving the oil and water repellancy of fabrics such as conventional polymerizable synthetic resins, silicones, and compounds having perfluorinated chain radicals and unsaturated polymerizable radicals. The oil and water repellancy of the treated fabrics is enhanced by the addition of the precondensates of the invention to the treating solution, and the repellancy properties of the fabric show better resistance to laundering and dry cleanmg.

It is a particular advantage of textile finishing baths including N-alkyl-N',N-alkylene ureas and the pre-ccndensates of the invention that they do not readily form coatings on the rolls of the padding machine during continuous impregnation of fabric with the finishing solution. The bath is usually covered by a foam in which the solid particles are so finely divided that the treated goods are not stained, and that the hue of fabrics dyed in solid colors is not dulled.

The finishing baths in which the solubility of the alkylalkylene urea is improved by the pre-condensate of the invention are less sensitive to elevated temperatures than similar solutions without the pre-condensates. The pad ding solutions may be employed at a temperature higher by 20 to 25 C. than those conventionally used, and working temperatures of 60 to C. are entirely practical without impairing the stability of the dispersions.

The concentrated mixtures of the N-alkyl-N',N'-alltylene ureas with the pro-condensates of the invention are relatively insensitive to elevated temperature. They may be safely stored, for example, for three days at 30 to 40 C., and yet be readily diluted to form stable treating baths.

The concentrated mixtures are combined with 10 to 30 percent of a weak organic acid such as acetic acid calculated on the weight of the N-alkyl-N',N-alkylene urea and then diluted to the desired concentration with water having a temperature of 20 to 30 C. The slightly acid dilute solutions or dispersions obtained are surprisingly stable and may be kept for several days without significant increase in the particle size of the dispersed phase and without deterioration of the finish product on textiles with such stored diluted solutions or dispersions.

The treating solution is preferably adjusted to a concentration of approximately 1 to 20 g. N-alkyl--N',N'- alkylene urea per liter of solution. The textile material is impregnated with the solution, and dried, and the resin material on the fabric is ultimately subjected to condensation in order to cure the acid soluble pre-condensate of the invention and to make it insoluble and hydrophobic. The final condensation is performed by heating the fabric in the usual manner to a temperature above 100 C.', and preferably to 120 to 160 C. for periods varying between approximately twenty minutes and one minute.

The treated fabrics show excellent water resistance and have a soft, pleasant hand.

The treating baths of the invention may contain additional finishing materials. Water repellancy agents such as wax or parafiin dispersions which may contain metal salts, formaldehyde resin pre-condensates together with acid or acid generating catalyst materials, optical bleaches, stifieners and starches are examples of such finishing materials.

The textile materials which may be treated to advantage with N-alkyl-N',N'-alkylene urea dispersions mixed with the pre-condensates of the invention include woven and knit goods, also felt and other non-woven fabrics, threads, yarns, loose fibers, and other intermediate products obtained during manufacture of fabrics from fibers. These textile materials may consist of natural or synthetic fibrous material. Particularly favorable elfects are achieved in the treatment of fibers and fibrous materials consisting of polyester resins, polyamides, polyacrylonitrile and its copolymers, natural, regenerated, and chemically modified cellulose. The most striking results are obtained with native cellulosic fiber material and with regenerated cellulose fibers, such as rayon.

The following examples are further illustrative of the present invention, and it will be understood that the invention is not limited thereto. All parts are parts by weight unless otherwise stated.

Example I 90 parts by weight of stearic acid are melted by heating to a temperature above 60 C. in a three neck flask equipped with a condenser, a stirrer, and a thermometer. 148 parts of methanol, 75 parts of paraformaldehyde, and 25 parts of melamine are added to the molten stearic acid while a temperature of approximately 60 C. is maintained, and the mixture is being stirred. After the reagents are mixed, the temperature is gradually raised to 120 within about two hours, and further to 130 within an additional hour. Methanol is permitted to distill off during heating. 25 parts of triethanolamine are then added whereby the temperature is dropped to about 115. This temperature is maintained, and stirring is continued until a sample of the reaction mixture is completely soluble in hot aqueous 6 percent acetic acid.

When this stage is reached, 190 parts of trichloroethylene are mixed with the reaction product. A clear solution is obtained and is poured into a container in which it is permitted to cool. When mixed with 10 to percent acetic acid in the form of a fairly strong aqueous acetic acid solution, the solution, which is a brownish liquid, may be diluted with water to form a very finely dispersed emulsion. When large quantities of the emulsion are to be prepared, the use of a mechanical agitator rotating at a rapid rate is preferred.

Example II 370 parts methanol, 69 parts triethanolamine, 187 parts paraformaldehydc, and 63 parts melamine are mixed by stirring in a three neck flask equipped with a condenser, an agitator, and a thermometer. While stirring is continued, the temperature of the mixture is slowly raised to 40 C. when 225 parts of a technical grade of stearic acid anhydride, having an acid value between 3 and 7, are added. The temperature is further raised to 120 C. within about two to three hours while the alcohol is permitted to distill ofi. A temperature of about 120 C. is maintained until the reaction product is clearly soluble in hot 6 percent acetic acid, whereupon it is mixed with 475 parts trichloroethylene.

The brownish liquid obtained can be readily emulsified in water by stirring if 10 to 15 percent of acetic acid are added. The droplets of the organic phase of the emulsion are extremely small.

Example III 324 grams hexamethylol melamine are finely pulverized. The powder obtained is stirred into a mixture of 2000 milliliters methanol and 100 milliliters concentrated hydrochloric acid. It dissolves completely within about ten minutes. Anhydrous sodium carbonate is added to the mixture until it is neutral to litmus paper. 160 gr. of carbonate are require Sodium chloride is precipitated and is filtered oil. The filtrate is evaporated in a vacuum to a concentration of approximately 99 percent. The residue which is of sirupy consistency is filtered hot to remove an additional amount of salt. The filtered residue consists essentially of the methyl ether of methylol melamine, or hexaltls(methoxymethyl)-melamine.

One part (by weight) of the perature of 180 to 200 ether is heated to stem- C. with about 1.3 parts of stearic acid at a pressure of 10 to 20 millimeters mercury until the reaction product has an acid value of 5 to 8. 90 parts of the latter reaction product are heated with 15 parts of triethanolamine with good agitation to a temperature of 115 to 120 C. at a pressure of 10 to 20 mm. mercury until a sample of the reaction mixture is soluble in warm diluted acetic acid. This requires heating for about one hour.

The reaction mixture or pro-condensate which is brownish yellow in color and the sample of which solidifies into a mass of waxy consistency, is mixed while still hot and liquid with 110 parts of tetrachlorethylene.- The resulting clear solution can be dispersed in water to form an emulsion in the presence of 20 to 30% by weight of acetic acid.

Example IV In a three neck flask as described in Example I, 182 parts by weight of methanol, 35 parts of triethanolamine, 90 parts of paraformaldehyde, and 190 parts of a technical grade of l,3-diamino-5-hexadecyl-2,4,6-trlazine are mixed. The technical mixture consists of of the pure compound, while the remainder is essentially a mixture of fatty acid nitriles having an average molecular weight of 255.

The contents of the fiask are heated within -2 to 3 hours to a temperature of 140 to 145 C. and the methanol is permitted to distill oif. Heating is continued until a sample of the pre-condensate is completely soluble in hot 6% aqueous acetic acid. It is then permitted to cool to C., and 260 parts of trichloroethylene are added. The resulting light yellow solution can be readily dispersed in water in the presence of 15 to 30% of its weight of acetic acid, and an emulsion in which the dispersed phase is very finely distributed is obtained.

Example V parts by weight of a dipalmityl melamine obtained by replacing two hydrogen atoms in the amino groups of melamine by the monovalent radical C H CO- of palmitic acid are mixed with 55 parts paraformaldehyde, 200 parts propanol, and 20 parts triisopropanolamine in the manner described in Example IV and to a temperature of to C. When a sample of the reaction mixture is found soluble in aqueous 10 percent acetic acid, parts monochlorobenzene are added. The solution obtained is .readily emulsifiable in water in the presence of 20 to 30% of acetic acid.

Example VI The three necks of a flask are respectively fitted with a stirrer, a reflux condenser, and a thermometer. 525 gr. of isobutanol are mixed inthe flask with 35 gr. of diethanolamine, 90 gr. of paraformaldehyde and 150 gr. of the reaction product obtained by heating one mol equivalent of melamine with two mols equivalents of heptadecylisocyanate at 240 C. The mixture is refluxed for three hours.

The reflux condenser is replaced by a descending condenser and the temperature is gradually raised to 150 to 155 over a period of two to three hours while the alcohol is distilled off. The maximum temperature is maintained until a sample of the product is soluble in hot 6 percent aqueous acetic acid. The main body of the precondensate is cooled to about 110 C. and is mixed with 240 gr. of toluene.

A nearly optically clear, light brown solution is obtained which forms a stable dispersion when mixed with water in the presence of 12 to 30 percent of acetic acid.

Example VII 170 gr. of a technical grade of stearo-guanamine, 90 gr. of paraformaldehyde, and 180 gr. of methanol are stirred in a vessel equipped with a reflux condenser until a clear solution is obtained. The technical stearo-guanamine contains 88 percent of the pure compound whereas the remainder consists essentially of stearyl nitrile. The solution is permitted to cool to 50 C. and 30 milliliters of a 15 percent solution of hydrochloric acid in methanol are added. The mixture is heated to the boiling point for five minutes, and then neutralized against litmus paper by the addition of anhydrous sodium carbonate.

The methanol is distilled off in a vacuum, the residue is taken up in benzene, and the benzene solution is filtered while hot. The benzene is evaporated from the filtrate in avacuum.

The residue consists of methylated methylol-stearoguanamine containing approximately 60 percent stearoguanamine. 150 parts of the residue are reacted with 21 parts by weight of triethanolamine at a temperature of 140 to 145 C. until a sample of the product forms a clear solution in hot 6 percent acetic acid. The main body of the product is permited to cool to 80 C. and mixed with an equal volume of a solvent mixture consisting of one part by volume of tetrachlorethylene and three parts by volume of benzene.

Example VIII 45 parts by weight of the triglyceride of ricinoleic acid which is etherified with 30 mol equivalents of ethylene oxide are dissolved in 126.5 parts of distilled water to which 15 parts of concentrated ammonium hydroxide solution (d.=0.90) are added. The solution is mixed at 20 C. with 28.5 parts by weight of ethylene imine diluted with 125 parts of distilled water. 200 parts octadecyl isocyanate are added drop by drop to the mixture under agitation and strong cooling. After the reaction is completed, 450 parts distilled water and parts concentrated ammonium hydroxide solution are added, and the resulting liquid is mechanically homogenized by means of a high speed stirrer. The total weight of the emulsion so produced is raised to 1,000 parts by the addition of a solution of 66 parts by weight of octadecyl-oxymethyleneoxyethyl morpholinium chloride in 134 parts distilled water.

50 parts by weight of the trichloroethylene solution of the acid soluble pre-condensate prepared in Example I are added to the emulsion which is then homogenized on a colloid mill. The homogenized emulsion may readily be diluted with water at temperatures between 20 and 40 C. when mixed with 7 percent acetic acid which is preferably admixed with stirring in the form of an aqueous solution containing 50 to 70 percent acetic acid.

Example IX A homogenized emulsion is prepared in the manner described in Example VIII, but 180 parts hexadecyl isocyanate are substituted for the 200 parts of octadecyl isocyanate. When stored tor an extended period, the emulsion thickens and becomes quite viscous. Yet, it can be readily diluted to a working concentration by the addition of acetic acid and water as described above.

Example X A mixture is prepared from 250 parts by weight of water, 15 parts of concentrated ammonium hydroxide solution (d.=0.90), 28.5 parts of ethylenimine, and 45 parts of the polyglycol ether of ricinolein obtained by reaction 30 mols of ethylene oxide with one mol of the glyceride of ricinoleic acid. The mixture is added drop by drop with vigorous agitation to 200 parts of heptadecyl isocyanate.

After the reaction has gone to completion, a mixture of 10 parts of concentrated ammonium hydroxide solution with 450 parts of water is added. A dispersion is formed and is homogenized by means of a high speed stirrer, while a solution of 66 parts of hexadecyloxymethyleneogyd etdhyl-morpholinium chloride in 134 parts of water is a e The resulting emulsion becomes very viscous in storage and cannot readily be diluted. When water is added, a precipitate forms and produces stains on fabrics treated with the emulsion. The tendency of the solution to form a precipitate and the resulting difficulties may be avoided by adding to the emulsion 25 parts of the trichloroethylene solution of Example IV either immediately after the emulsion was prepared or prior to diluting. When 5 percent acetic acid is added, the emulsion containing the precondensate of Example IV may be diluted readily without the formation of a precipitate.

Example XII The triglyceride of ricinoleic acid is etherifled with 30 mol equivalents of ethylene oxide. 45 parts of the resultmg glycol ether are dissolved in 126.5 parts of distilled water together with 3 parts of potassium carbonate. The solution is mixed at 20 C. with 28.5 parts ethylenimine diluted with parts distilled water. 200 parts octadecyl isocyanate are added drop by drop with agitation and cooling. After the reaction has been completed, 450 parts distilled water and 2 parts potassium carbonate are added, and the mixture is mechanically homogenized by means of a high speed stirrer. It is made up to 1,000 parts by addition of a solution of 66 parts of octadecyloxymethylene-pyridinium chloride in 134 parts of distilled water.

7 parts of the chlorobenzene solution prepared according to the method of Example V are added to the homogenizate, and the mixture is run through a colloid mill. The emulsion formed may readily be diluted with water at temperatures between 20 and 40 C. after the addition of 3 percent of acetic acid, preferably in the form of a strong gcetic acid solution containing 50 to 70 percent of t e aci Example XIII An ether of stearyl alcohol (octadecanol) and polyethylene-glycol is prepared from the stearyl alcohol by reaction with twenty mol equivalents of ethylene oxide. 40 parts of the ether are mixed with 250 parts of water, 15 parts by weight of an aqueous concentrated ammonium hydroxide solution (d. 0.90), and 37.5 parts of propylene imine (C-methyl-ethylenimine). The mixture is added drop by drop with vigorous stirring to 200 parts by weight of octadecyl isocyanate. After the reaction has been completed, a mixture of 10 parts concentrated ammonium hydroxide solution and 450 parts water is added. The resulting dispersion is homogenized by means of a high speed stirrer and diluted with a solution of 66 parts of hexadecyl-oxymethylene-pyridinium chloride in 134 parts of water.

An emulsion is obtained. Its viscosity increases so much in a few weeks storage that it cannot readily be diluted with water. When a measure of dilution is achieved, a permanent precipitate is formed and stains fabrics treated with the diluted emulsion.

Addition of 15 parts of the toluene solution obtained by the method of Example VI either immediately after preparation of the emulsion, or shortly before dilution permits the emulsion to be diluted in the presence of percent acetic acid without difiiculty and without precipitation of stain producing material.

Example XI V Ricinolein is etherified with 30 mol equivalents of ethylene oxide. A solution of 45 parts by weight of the polyethyleneglycol-ether so produced in 126.5 parts of distilled water mixed with 15 parts by weight of concentrated ammonium hydroxide solution (d. 0.90) is combined at 20 C. with a mixture of 28.5 parts of ethylenimine and 125 parts of distilled water. 200 parts of octadecyl isocyanate are added to the solution drop by drop with stirring and intensive cooling.

After the reaction has come to an end, 450 parts distilled water and parts by weight of concentrated ammonium hydroxide are added, and the mixture is homogenized by means of a high speed stirrer. It is made up to 1,000 parts by means of a solution of 66 parts of octadecyl-oxymethylene-pyridinium chloride in 134 parts of distilled water.

40 parts of the mixed solvent solution of Example VII are added and the product is run through a colloid mill. The emulsion formed may be diluted with Water at 20 to 40 C. as desired after the addition of 7 percent acetic acid, preferably in the form of an aqueous acetic solution having a concentration of 50 to 70 percent.

Example XV 10 grams of the homogenized emulsion produced by the method of Example VIII are diluted with water in the presence of acetic acid to make one liter. Cotton poplin is soaked in the aqueous liquid and squeezed between rollers to a pick-up of about 80 percent. The fabric is dried at 100 C. and then cured at about 140 C. for three minutes.

The water absorption of the treated poplin is greatly reduced, and it has acquired an excellent soft hand. Neither the water resistance nor the texture f the fabric are affected by commercial washing and dry-cleaning procedures.

In addition to the afore-mentioned homogenized emulsion, the treating bath may also contain 100 g. of a 50 percent aqueous solution of dimethylol-ethylene-urea and 10 g. magnesium chloride hydrate. The additional materials impart crease resistance to the fabric without impairing its water resistance and hand.

Example XVI A rayon gabardine is saturated with a bath containing 30 grams per liter of the homogenized emulsion prepared according to the method of Example X and diluted in the presence of acetic acid. The gabardine is squeezed be tween rollers to a pick-up of 100 percent, dried at 110 C., and cured ten minutes at about 130 C.

The treated material absorbs substantially less water than the original rayon gabardine, and has a pleasant soft hand.

When treating baths are prepared by dilution of the emulsions resulting from the processes described in Ex- 10 amples IX and XI to XIV, and cotton or rayon fabrics are treated in such baths in the manner described in Examples XV and XVI, treated fabrics having improved qualities as to water absorption and texture are obtained.

It will be appreciated that the method is not limited to woven fabrics, nor to fabrics as such, but may be applied, for example, to felt and other non-woven fabrics, to yarns and to other fibrous material. While cotton and other cellulosic fibers respond most favorably to the treatment, the invention is not limited to any specific substrate except as specifically defined in the appended claims.

Obviously, many modifications and variations of the present invention are possible in the light of the above teachings. It is therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

What we claim is:

1. A product for treating textiles which comprises the combination of an aqueous dispersion containing N-alkyl-NN'-alkylene urea, wherein the alkyl radical has at least ten carbon atoms, and the alkylene radical has between two and three carbon atoms; with awater insoluble pre-condensate of an aminotriazine having at least two amino radicals and being free of hydroxyl radicals directly bound to the triazine nucleus, with formaldehyde and a lower monohydric alkanol having between one and five carbons atoms, said pie-condensate being soluble in organic solvents and in dilute aqueous solutions of lower monocarboxylic alkanoic acids, and said pro-condensate per triazinyl radical having at least one aliphatic radical of more than ten carbons atoms and at least 0.2 mol equivalent of basic amino groups of an alkanolamine of the formula wherein R is a radical selected from the group consisting of hydrogen, hydroxyalkyl radicals having two to four carbon atoms, alkyl radicals having one to four carbon atoms, and the radicals -CH -CH --NR R and CH CH CH NR R R is a hydroxyalkyl radical having two to four carbon atoms; and R is selected from the group consisting of hydrogen and hydroxyalkyl radicals having two to four carbon atoms; said dispersion containing 0.2 to 40% by weight of said pre-condensate relative to said N-alkyl-N,N"-alkylene urea, and an amount of a liquid organic solvent free of hydroxyl groups and substantially insoluble in water, said pre-condensate amounting to approximately 25 percent to 75 percent of the combined weight of said precondensate and of said solvent.

2. A product according to claim 1, wherein said aminotriazine is melamine, and said aliphatic radical of more than ten carbon atoms is an aliphatic radical of fifteen to nineteen carbon atoms.

3. A product according to claim 1 wherein said precondensate is obtained by reacting an aminotriazine having at least two amino radicals and free of hydroxyl radicals directly bound to the triazine nucleus, with formaldehyde, a lower monohydric alkanol, a fatty acid compound selected from the group consisting of fatty acids having an alkyl radical of 15 to 19 carbon atoms and anhydrides of said fatty acids, and an alkanolamine of the formula until the reaction product is soluble in a hot dilute aqueous solution of a lower monocarboxylic alkanoic acid.

4. A product according to claim 3, wherein said R-ITT-Rr 2 wherein R is a radical selected from the group consisting of hydrogen, hydroxyalkyl radicals having two to four carbon atoms, alkyl radicals having one to four carbon atoms, and the radicals -CI-I -CH -NR R and -CH -CH -CH -NR R R is a hydroxyalkyl radical having two to four carbon atoms; and R is selected from the group consisting of hydrogen and hydroxyalkyl radicals having two to four carbon atoms, at a temperature substantially between 130 C. and 160 C. until the reaction product is soluble in a hot dilute aqueous solution of a lower monocarboxylic alkanoic acid.

6. A product according to claim 1 wherein said precondensate is obtained by reacting and aminotriazine derivative which results by heating one mol of a compound of the formula wherein Z, is hydrogen, amino radical, alkyl radical with 1 to 22 carbon atoms; with at least 1 mol of an alkyl isocyanate, the alkyl radical has 15 to 19 carbon atoms per mol of said compound and at most l moi of said alkyl isocyanate per equivalent of amino radicals at temperatures between 200 C.- and 260 C.; with formaldehyde, a lower monohydric alkanol, and an alkanoiamine of the formula R-III-Rr R2 wherein R is a radical selected from the group consisting of hydrogen, hydroxyalkyl radicals having two to four carbon atoms, alkyl radicals having one to four carbon atoms, and the radicals --CH --CH --NR R and -CH CH -CH -NR R R is a hydroxyalkyl radical having two to four carbon atoms; and R is selected from the group consisting of hydrogen and hydroxyalkyl radicals having two to four carbon atoms, at a temperature substantially between C. and C. until the reaction product is soluble in a hot dilute aqueous solution of a lower monocarboxylic alkanoic acid.

7. A textile material treated by being impregnated with the product of claim 1 and subsequent drying and curing.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A PRODUCT FOR TREATING TEXTILES WHICH COMPRISES THE COMBINATION OF AN AQUEOUS DISPERSION CONTAINING N-ALKYL-N''N''-ALKYLENE UREA, WHEREIN THE ALKYL RADICAL HAS AT LEAST TEN CARBON ATOMS, AND THE ALKYLENE RADICAL HAS BETWEEN TWO AND THREE CARBON ATOMS; WITH A WATER INSOLUBLE PRE-CONDENSATE OF AN AMINOTRIAZINE HAVING AT LEAST TWO AMINO RADICALS AND BEING FREE OF HYDROXYL RADICALS DIRECTLY BOUND TO THE TRIAZINE NUCLEUS, WITH FORMALDEHYDE AND A LOWER MONOHYDRIC ALKANOL HAVING BETWEEN ONE AND FIVE CARBONS ATOMS, SAID PRE-CONDENSATE BEING SOLUBLE IN ORGANIC SOLVENTS AND IN DILUTE AQUEOUS SOLUTIONS OF LOWER MONOCARBOXYLIC ALKANOIC ACIDS, AND SAID PRE-CONDENSATE PER TRIAZINYL RADICAL HAVING AT LEAST ONE ALIPHATIC RADICAL OF MORE THAN TEN CARBONS ATOMS AND AT LEAST 0.2 MOL EQUIVALENT OF BASIC AMINO GROUPS OF AN ALKANOLAMINE OF THE FORMULA 